JPS63161096A - Bulky granular detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high bulk density granular detergent composition having good solubility and a softening effect.

In order to improve solubility, conventional detergents are spray-dried into bead-like hollow particles with an average particle size of about 200 to 800 μm. As a result, the bulk density is as low as about 0.3 g/cc, which not only increases transportation costs but also requires a considerable amount of space for storage and display. In addition to this, there are other problems such as difficulty in storing the product and difficulty in measuring it even in ordinary households.

Therefore, there has been a need to develop a high bulk density detergent that can solve these drawbacks of current spray-dried detergents and enable cleaning with a small amount of detergent.

The present applicant has developed a method for producing a high bulk density detergent, in which the detergent raw materials are first intimately kneaded and mixed, the resulting kneaded material is crushed, and then coated with water-insoluble fine powder having an average-order diameter of 10 μm or less. (Japanese Unexamined Patent Publication No. 60-96698).

Furthermore, in addition to this, consumers are demanding detergents that clean clothes while also imparting flexibility, and various detergent compositions in which cationic surfactants are added to anionic surfactants have been proposed (especially JP-A-55-106299, JP-A-55-115499, JP-A-57-1
37396, etc.).

However, in such detergent compositions, the anionic surfactant and the cationic surfactant react in the washing liquid to form a complex, so that a sufficient softening effect cannot be obtained.

An object of the present invention is to obtain a high bulk density granular detergent composition that has good solubility and can impart flexibility to items to be washed.

The high bulk density granular detergent composition of the present invention has an amount of 0.5 to 1.2 g/
It has a bulk density of cc, and is characterized by containing the following components (A) and (B) in a weight ratio of (A)/(B) = 25/1 to 2/1.

(A) A crushed solid detergent obtained by kneading and mixing detergent raw materials is coated with inorganic fine powder of 10 μm or less, containing 20 to 50% by weight of a surfactant, Contains 15% by weight or more of linear alkylbenzene sulfonate, 10% or less of particles of 200 μm or less, 20
Detergent particles that are substantially free of particles larger than 0.00μL.

(B) A cationic surfactant represented by the general formula CI)
Cationic activator particles containing 0 to 90% by weight.

R,, R4 represents a C to C4 alkyl group, a benzyl group, a 02 to C4 hydroxyalkyl group or a polyoxyalkylene group, and X is a halogen, 1/2SO,
CH, SO,.

C2H, SO4 Or CH, -■-so□. ) The present invention will be explained in more detail below.

The granulated detergent particles of component (A) contain 20 to 40% by weight of a surfactant. If the content is less than 20% by weight, the cleaning power is low and there is a practical problem, and if the content exceeds 50% by weight, manufacturing becomes difficult. As the surfactant, at least 15% of linear alkylbenzene sulfonate is added to the granulated detergent particles.
It is necessary to incorporate it in an amount of at least 20% by weight, preferably at least 20% by weight.

If the amount of the linear alkylbenzene sulfonate is less than 15% by weight, the solubility is poor and the flexibility imparting effect is also poor. The linear alkylbenzene sulfonate preferably has an alkyl group having an average carbon number of 8 to 16.

All of the necessary amount of surfactant in the granulated detergent particles can be accounted for by the linear alkylbenzene sulfonate, but other surfactants such as anionic surfactants and nonionic surfactants can also be used in combination. .

Examples of such anionic surfactants include α-olefin sulfonates, α-sulfo fatty acid ester salts, alkyl sulfates, and alkyl ether sulfates.

Examples of nonionic surfactants include alcohol ethoxylates, alkylphenol ethoxylates, and among these, alcohol ethoxylates prepared by adding 8 to 30 moles of ethylene oxide to a primary or secondary alcohol having 8 to 18 carbon atoms are used. By adding 5% by weight, solubility can be significantly improved.

As a builder, the average represented by the general formula % formula % () (in the formula, M is Na or Na, x is 0.7 to 1.5, and y is an integer from 0.8 to 6.2) Zeolite having an ion exchange capacity with a particle size of 5 μm or less is suitable. Such zeolite captures calcium ions and magnesium ions, which are the hardness components in the cleaning liquid, through its ion exchange ability, contributing to improving the cleaning power, and is also effective in improving powder physical properties, especially preventing caking during storage.

In addition, water-soluble builders include phosphates such as sodium tripolyphosphate and sodium pyrophosphate, organic chelate builders such as trisodium nitrilotriacetate (NTA), trisodium citrate, and sodium ethylenediaminetetraacetate, polyacetal carboxylates, and acrylics. Polymer builders such as acid (hydroxyacrylic acid) polymers, acrylic acid-methacrylic acid copolymers, maleic anhydride-oleic acid copolymers, alkalis such as sodium carbonate, potassium carbonate, sodium silicate, and sodium borate. It is preferable to use a builder or the like. These builders have the ability to capture calcium ions and magnesium ions, or have an alkaline buffering ability.

Furthermore, anti-recontamination agents such as polyethylene glycol (PEG) and carboxymethyl cellulose (CMC),
Reducing agents such as NaHSO, Na25O, alkaline protease, amylase.

Enzymes such as cellulase and lipase, as well as optical brighteners,
Glauber's salt, fragrances, etc. can also be added. These detergent components can also be mixed into powder after being crushed.

The granulated detergent particles of the present invention are produced by kneading and mixing each detergent component and then crushing the particles, as described in JP-A No. 60-96698, and then adding water with an average-order diameter of 10 μm or less. It can be manufactured by coating with insoluble fine powder. The detergent ingredients can also be supplied in the form of a spray-dried product and kneaded. The detergent particles obtained were 0.5 to 1.2 g/
It has a bulk density of approximately cc.

The compacted detergent raw material homogeneously kneaded with a kneader or the like is then crushed and granulated with a crusher. During crushing, the temperature of the crushed material increases due to frictional heat, so it is preferable to introduce cold air into the crusher for treatment.

Shredding can be done by using a crusher that has a classification function such as screen classification or wind classification, or by classifying the crushed material with a sieve or the like and recycling unintended particles. It is desirable to granulate in a distributed manner. The crusher has multi-stage rotating crushing blades and can crush 360 pieces of material.
6, which is discharged through a release screen. This type of crusher can set an arbitrary upper limit particle size by adjusting the screen opening, and prevents over-grinding by shortening the residence time of the crushed material in the crushing chamber, reducing the amount of fine powder. A sharp particle size distribution with significantly less particles can be obtained. It can also be crushed using an extrusion granulation method in which the kneaded material is extruded and then cut into pieces.

Can be granulated.

The granulated product obtained by crushing is then coated with water-insoluble fine powder to undergo surface modification.

As the water-insoluble fine powder, the average-order diameter is 10 μm or less,
Preferably, one with a diameter of 4 μm or less is used. If the particle size is too large, the coating will not be uniform and, as a result, the fluidity and storage stability will not be improved.

As a coating device, a transfer type, a fluidized bed type, a mixing type, etc. are all used, and the water-insoluble fine powder adheres to the surface of the granulated product. The amount of water-insoluble fine powder added during coating is preferably 0.5 to 5% by weight based on the granulated product. Specific examples of the water-insoluble fine powder include calcium stearate, magnesium stearate, aluminosilicates such as A-type zeolite, calcium carbonate, magnesium carbonate, magnesium silicate, silicon dioxide (white carbon), and titanium dioxide. By coating in this manner, adhesion between detergent particles is suppressed and blocking due to storage is prevented. In addition, the coating of fine powder improves the surface properties, improves fluidity, and allows excess moisture to remain within the particles.
Solubility is improved.

Furthermore, the granular detergent obtained in the above manner may be mixed with a cationic surfactant as it is after adding trace ingredients such as perfume, or may be mixed with a cationic surfactant as it is, or Marumerizer (Fuji Powdal)
), the particles can be sized by being entrained in an air current, guided into a cyclone-like device, and brought into contact with a wall surface, so that the shape of each particle becomes approximately spherical, or the moisture content can be adjusted by slightly drying with hot air.

As component (B) of the present invention, cationic surfactant particles containing 20 to 90% by weight of a cationic surfactant represented by the following general formula (I) are used.

R3, R, represents a C1-C4 alkyl group, benzyl group, C2-C4 hydroxyalkyl group or polyoxyalkylene group, X is halogen, 1/2SO4,
CH, So4°C, H, So.

Or CH, -■-803. ) Specific examples of these cationic surfactants include: 1) distearyldimethylammonium salt, 2) dihydrogenated tallow alkyldimethylammonium salt, 3) dihydrogenated palmalkyldimethylammonium salt, 4) distearylmethyl Hydroxyethylammonium salt.

5) distearyldihydroxyethylammonium salt, and the like. Further, specific examples of halogen as a counter ion include chloride, bromide, and the like.

The cationic surfactant particles contain 20 to 90% by weight of the above-mentioned cationic surfactant, and may also contain nonionic cellulose derivatives such as methyl cellulose, and inorganic compounds such as white carbon, calcium carbonate, and zeolite. Improve flexibility and powder properties. It is also used after being agglomerated using a binder such as a nonionic surfactant or polyethylene glycol. If the amount of the cationic surfactant is less than 20% by weight, the flexibility imparting effect will be insufficient. On the other hand, if it exceeds 90% by weight, foaming will deteriorate, which is not preferable.

The cationic activator particles of the component (B) are preferably mixed with the detergent particles of the component (A) in the form of particles with a particle size of about 50 to 1000 μm by crushing granulation, spray cooling, etc.
Furthermore, granulation can also be carried out using a binder or the like.

There are various methods for pulverizing cationic surfactant particles, including heating and melting the cationic surfactant, adding and mixing nonionic cellulose derivatives and inorganic compounds therein, spray cooling, or cooling and solidifying. , a method of crushing and granulating;
There is a method in which a cationic surfactant, a nonionic cellulose derivative, and an inorganic compound are mixed in a kneader or the like at room temperature, and then crushed and granulated. By adding a nonionic cellulose derivative and an inorganic compound, they can be kneaded into the surface of the cationic surfactant particles.

Furthermore, after granulating in this manner, desired additives such as zeolite can be added, a binder can be added, and granulation can be carried out again.

It is preferable to use granular additives such as nonionic cellulose and inorganic compounds with an average particle size of 500 μI or less.

If the particle size becomes large, it is not only difficult to uniformly impart a softening effect to the surface of the object to be washed, but also the additive particles may sometimes adhere to the object to be washed as they are after washing, which is undesirable.

The mixing ratio of (A) detergent particles and (B) cationic activator particles is in the range of (A)/(B) = 25/1 to 2/1, preferably 10/1 to 4/1 in terms of weight ratio. There is a need to. If the ratio of cationic activator particles is less than 25/1, the flexibility imparting effect will be poor, while if it exceeds 2/1, the detergency will decrease and it will also be disadvantageous in terms of cost.

Further, the bulk density of the mixture of components (A) and (B) needs to be 0.5 to 1.2 g/cc from the viewpoint of solubility and storage space (compactness).

Furthermore, it is important that the particle size distribution of (A) detergent particles is such that particles of 200 μm or less are 10% or less and particles of 2000 μm or more are not substantially included. 200μ
If 10% or more of fine particles with a diameter of m or less are present, these will react with the cationic activator particles, resulting in a decrease in flexibility, and the fluidity of the particles as a whole will deteriorate. On the other hand, 200
If particles of 0 μm or more are present, they will not completely dissolve during washing and will adhere to the items to be washed, so-called cloth adhesion, which will not only give a bad impression to consumers but also reduce the cleaning power.

According to the present invention, detergent particles containing 15% by weight or more of a linear alkylbenzene sulfonate and having a specific particle size distribution and cationic surfactant particles are mixed in a specific ratio. It is possible to obtain a high bulk density granular detergent composition that has good solubility, has an excellent softening effect, and is prevented from adhering to fabric.

EXAMPLES Hereinafter, the effects of the present invention will be explained in more detail with reference to Examples. Prior to this, evaluation methods used in Examples are shown below.

1 using granular detergent and tap water at 60°C.
After washing for 5 minutes, the test fabric is pretreated by rinsing it three times for 3 minutes each using tap water at 60°C. Next, this test cloth was placed in a jet-type domestic electric washing machine, and using the high bulk density granular detergent shown in Table 1 below and 30 Q of tap water at 25°C, 30 g of the high bulk density detergent composition and 30 times the bath ratio were washed. After washing for 10 minutes under the following conditions and dehydrating for 1 minute, rinsing with tap water at 25° C. for 3 minutes and dehydrating for 1 minute was repeated twice. After that, the test cloth was air-dried for 24 hours and then dried at 25℃ and 65% RH.
The air-dried test fabric was conditioned under the following conditions.

A cotton towel was taken out of the test fabric thus obtained, and its feel was judged by five judges, and the softening effect of the high bulk density granular detergent composition was evaluated from the average of the five judges. In addition, this feel evaluation was performed based on the following criteria and compared with the feel of a cotton towel obtained by the same procedure as above except that a detergent composition containing no cationic surfactant particles was used. Ta.

Extremely soft 5 points Fairly soft 4 points Soft 3 points Slightly soft 2 points Slightly soft 1 point Cloth attached Particle multiplicity Black nylon slip 80g x 2 black acrylic sweaters 180g x 2 blue cotton knitted shirts 100g x 5 pieces laundry After washing for 5 minutes using a high bulk density detergent composition and tap water at 5°C at a bath ratio of 30, wash the washing machine at 5°C.
The items were rinsed twice for 3 minutes each in tap water to dehydrate them, and the amount of particles adhering to the items to be washed was visually determined using the following criteria.

No adhered particles are observed 0 Adhered particles are slightly noticeable Δ Adhered particles are extremely noticeable × Fill Hoshihara Ubicar with water IQ at 25°C, and insert the cell for measuring conductivity into it. Next, 1 g of each detergent composition particle having the composition shown in Table 1 was added to water, and the mixture was stirred at a speed of 250 rpm using a constant speed Starsea, and the conductivity was determined as the time required for 90% of the added detergent particles to dissolve. Measured from the change, T,
. (seconds).

Here, in terms of conductivity, HORIBA CONDUC
TIVEMETER DS-8F type was used.

Example <Preparation of detergent particles> Each component was uniformly kneaded using a kneader so that the detergent particle composition shown in Table 1 below was obtained.

The obtained uniform kneaded product was in the form of a sheet with a thickness of 3 mm and a width of 50 mm, and the temperature was 50 to 55°C.

To make it easier to crush, put it into a pelleter (Fuji powder pelleter double EXDF-60) and
It was made into a cylindrical pellet of 5n+m. The temperature of the pellet product was the same as that of the kneaded product, and it was discharged at 50 to 55°C. This pellet was quantitatively fed to a crusher (Okada Sei Nispeed Mill NO-30). At this time, 15° C. cold air was introduced together with the crushed material at a ratio of 1512/kg of crushed material. The crusher rotated four stages of crushing blades with a diameter of 15 cm at 300 rpm, and the screen was made of punching metal with a diameter of 2 mm and an aperture ratio of 20%.

Next, 97 parts by weight of the obtained crushed product and an average particle size of 3 μm
A transfer drum (D = 30
cmφ*L=60cm), and 30rp
Hl was coated with a distillation time of 5 minutes and had the composition and particle size distribution shown in Table 1, with a bulk density of 0.8 to 0.9 (g/
cc) detergent particles (component A) were obtained.

Preparation of cationically active particles> Dihydrogenated beef tallow alkyl dimethyl ammonium chloride (Alucard 2HT, purity 93%) was melted at 120°C, nonionic cellulose derivative powder (methylcellulose to Alucard 2HT 1%) was added, and after cooling, An inorganic compound powder (20% of finely ground mirabilite to block) is added to the block and pulverized to an average particle size of about 80 μm.

Furthermore, 100 parts of this pulverized material was blended with 120 parts of white carbon, calcium carbonate, and zeolite, and 70 parts of a liquid binder was sprayed to form an agglomerate, resulting in an average particle size of 400 parts.
The particles were made into μm particles. here.

As a liquid binder, polyethylene glycol (P
An 80% aqueous solution of an ethylene oxide adduct (average number of moles added: 8.6) of nonylphenol and nonylphenol was used.

The resulting cationic surfactant particles contain 27% by weight of cationic surfactant.

Preparation of high bulk density granular detergent composition> The detergent particles obtained as described above and cationic activator particles were powder mixed in the ratio shown in Table 1 to prepare a high bulk density granular detergent composition. did. The bulk density of this mixture is shown in Table-1.

Next, each composition was evaluated for flexibility, fabric adhesion, and solubility, and the results are shown in Table 1.

The abbreviations and details in the detergent particle composition in Table 1 are as follows.

LAS: Sodium linear alkylbenzenesulfonate having an alkyl group having 10 to 14 carbon atoms AO8: Sodium α-olefin sulfonate having 14 to 18 carbon atoms AS: Sodium salt of synthetic alcohol sulfate having 12 to 13 carbon atoms α-8F : α-sulfohated beef tallow fatty acid methyl ester soda salt nonionic: C1, ~1. 15 mole adduct of primary alcohol with EO Carbonate-Na: Soda carbonate (reagent) Carbonate-K: Potassium carbonate (reagent) Zeolite di-synthetic human-shaped zeolite (Mizusawa Chemical "Jilton BJ") (The following is the margin)

Claims (1)

[Claims] 1. The following components (A) and (B) in a weight ratio of (A)/
A high bulk density granular detergent composition having a bulk density of 0.5 to 1.2 g/cc, characterized in that it contains (B) in a ratio of 25/1 to 2/1. (A) A crushed solid detergent obtained by kneading and mixing detergent raw materials is coated with inorganic fine powder with an average particle size of 10 μm or less, and contains 20 to 50% by weight of a surfactant, and contains 15% by weight or more of a linear alkylbenzene sulfonate, and has a diameter of 200 μm.
Detergent particles containing 10% or less of the following particles and substantially free of particles larger than 2000 μm. (B) Cationic surfactant particles containing 20 to 90% by weight of a cationic surfactant represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (However, R_1 and R_2 represent C_1_2 to C_2_6 alkyl groups, and R_3 and R_4 are C_1 to C_4 alkyl groups, benzyl groups, and C_2 to C_4 hydroxyalkyl groups. or a polyoxyalkylene group, where X is halogen, 1/2SO_4, CH_3SO_4, C_2H
＿５SO＿４ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼
shows. )